Reaction of allyl derivatives with carbon monoxide and 1,3 - dienic olefins



United States Patent US. Cl. 260-408 6 Claims ABSTRACT OF THE DISCLOSUREA process is provided for preparing 3,7-dienoyl halides, which comprisesreacting a ,8,'y unsaturated alkylene halide with carbon monoxide and a1,3-dienyl olefin at a temperature within the range from about to about250 C. at which reaction proceeds, below the decomposition temperatureof the reactants and reaction products, under a pressure within therange from about 1 to about 300 atmospheres in the presence of aplatinum-palladium triad catalyst.

This application is a division of application Ser. No. 496,686, filedOct. 15, 1965, and now abandoned.

This invention relates to a process for preparing 3,7- dienoyl halidesby reacting allylic halides with carbon monoxide and 1,3-diene olefinsin the presence of a platinum or palladium triad catalyst, and moreparticularly to a process for reacting allylic halides with carbonmonoxide and butadiene in the presence of palladous chloride to produce3,7-octadienoyl halides in good yield.

Chiusoli, Gazz. Chim. Ital, 89, 1332-1337 (1959), US. Pat. No.3,146,256, dated Aug. 25, 1964, has described the synthesis ofmono-unsaturated carboxylic acids and esters from allyl chloroderivatives and carbon monoxide or from acetylene and carbon monoxide inthe presence of nickel carbonyl as a catalyst. Using allyl chloride asan exemplary, the reaction proceeds as follows:

l CHFCHCH2]QC1+ NiClz 4-- CO As the above reaction scheme shows, thenickel carbonyl takes part in the reaction, forming an intermediatenickel carbonyl complex with the allylic halide which can then bedecomposed by the action of carbon monoxide to form the correspondingacyl halide plus nickel chloride. The nickel chloride can be returned tonickel carbonyl by hydrolysis and reaction with carbon monoxide, andsometimes this takes place in the reaction mixture, but this reversereaction is not easy to control in a manner to obtain a quantitativeyield of the carbonyl. Consequently, as Chiusoli points out, aconsiderable proportion of nickel carbonyl is changed to nickelchloride, and due to this and the fact that only yields are obtainable,this reaction is not practical from the commercial standpoint as amethod for the preparation of acyl halides from allyl chloride. Thereaction is, however, of considerable theoretical interest, and it canbe carried out not only with carbon monoxide but also with acetylene,which enters into the molecule in the same relative position as thecarbonyl group.

When Chiusoli reacts allyl chloro-derivatives, carbon monoxide,acetylene, and water or alcohol in the presence 3,536,739 Patented Oct.27, 1970 of nickel carbonyl, there are formed unsaturated acids oresters according to the following equations:

Nickel carbonyl is partially replaced in this reaction, but the amountof nickel carbonyl added initially is fairly large, on a molar basisabout one-half of the amount of the allylic halide charged.

In accordance with the instant invention, 3,7-dienoyl halides areprepared from liq-unsaturated alkylene halides by reaction with carbonmonoxide and a 1,3- diene olefin in the presence of a platinum-palladiumtriad catalyst. The reaction proceeds under moderate conditions inaccordance with one of the following schemes, according to whether thereactant is a 1,3-diene, using butadiene as illustrative:

It will be apparent from the above that when butadiene is employed, thereaction product is a 3,7-dienoyl halide.

The reaction is applicable, as the above reaction scheme indicates, toany allylic or tin-unsaturated aliphatic halide having the formula setout in the first equation. In this formula, R R R R and R can behydrogen or an organic radical, such as an alkyl group having from oneto about nine carbon atoms; an aryl group having from six to aboutthirty carbon atoms, including aralkyl and alkaryl groups in which eachalkyl or alkylene substituent may have up to fifteen carbon atoms, andhaving from one to five such substituents per aryl nucleus; cycloalkylgroups having from six to about thirty carbon atoms, includingalkyl-substituted cycloalkyl groups in which each alkyl substituent hasup to about fifteen carbon atoms, halogen-substituted alkyl andcycloalkyl groups, the halotgen including chlorine, bromine, fluorine,and iodine; and ester-substituted alkyl, aryl and cycloalkyl groups, theester substituent being of the form COOR wherein R is as defined abovefor R R R R and R hydrogen excepted. X is halogen, including chlorine,bromine, fluorine, and iodine.

While for simplicity the reaction scheme is shown using any 1,3-dienecan be employed.

The 1,3-dienes can be defined by the formula:

m Rn R12 R13 wherein R to R are as defined above for R to R inclusive.

As exemplary of the alkyl substituents there can be mentioned methyl,ethyl, propyl, isopropyl, butyl, isobutyl, tertiary-butyl, isoamyln-arnyl, neopentyl, tertiaryamyl, isohexyl, 2-ethylhexyl, nonyl,isononyl, tertiarynonyl, and heptyl. Exemplary aryl, aralkyl and alkarylsubstituents include phenyl tolyl, xylyl, isononylphenyl,tertiaryoctylphenyl, dodecylphenyl, benzyl, a-phenethyl, B-phenethyl,pentadecylphenyl, mesityl, phenylphenyl, and naphthyl. Exemplarycycloalkyl groups include cyclo pentyl, cyclohexyl, and cycloheptyl.These substituents may include halogen, nitro and ester groups, such as,for example, chloroethyl, 4-bromocyclohexyl, nitrobenzyl, nitrophenyl,and acetylphenyl. Specific compounds include 1,4-dimethylbutadiene;2,5-dimethyl-2,4-hexadiene; 2,3-diemthylbutadiene;1,4-diphenylbutadiene; 1,4-dimethyl-1,4-diphenylbutadiene; isoprene;1,3-pentadiene; 4 bromocyclohexyl butadiene; acetylphenyl butadiene,etc.

The reaction preceeds in the presence of any platinum or palladium triadcatalyst, generically referred to in the claims as a platinum-palladiumtriad catalyst, including, for example, platinum, palladium, osmium,iridium, rhodium, and ruthenium. Compounds of these metals can, forinstance, be the salts, for example, the chloride, bromide, nitrate,sulfate, or acetate; the oxides; and organic complexes of the metal,such as for instance, the benzonitrile, bis-1r-allyl, or acetylacetonatecomplexes. The metal or the compound of the metal can be supported on aninert carrier such as carbon, alumina, or silica. The palladium halidesare particularly desirable because they are available and give excellentyield, and accordingly these are preferred, for instance, palladouschloride and palladous bromide.

Other exemplary catalysts are palladium on carbon; palladous oxide;palladous benzoate; bis(benzonitrile) palladous chloride; the chloridesor rhodium, ruthenium, platinum, iridium, and osmium; platinous acetate;rhodium oxide; palladous cyanide; rubidium carbonate; potassiumchloropalladite; and palladous acetylacetonate.

Compounds known to complex with the platium or palladium triad groupmeals can also be added as cocatalysts. Examples of such ligands includetriphenylphosphine, pyridine, benzonitrile, and pentane-1,3-dione. Smallamounts of such cocatalysts suffice to [give an improved effect. Amountswithin the range from about to about 500 mole percent based on theWeight of the catalyst can be used.

Exemplary [Ly-unsaturated aliphatic halides include allyl chloride,allyl bromide, ,B-methallyl chloride, 13- metallyl bromide, 'y-methallylchloride, y-methallyl bromide, l-phenyl-3-chloropropene-1,l-chloromethylcyclohexene, ethyl-2-chlorobutene-3,p-nitrocinnamylbromide, and bisallylic halides, such as1,4-dichloro-2-butene.

The amount of catalyst is in no way critical, and very small amountsgive effective results. Amounts within the range from about 0.001 tomolar percent based on the amount of the allylic halide can be used.Amounts within the range "from about 0.001 to 5 molar percent arepreferred. Two or more platinum-palladium triad catalysts can be used inadmixture for advantageous effects.

The carbon monoxide is conveniently introduced in gaseous form. Thereaction mixture containing the allylic halide is preferably in theliquid phase. In this event, the carbon monoxide can be bubbled into thereaction mixture, or, alternatively, if the carbon monoxide is used asan atmosphere, intermixed therewith by vigorous stirring of the reactionmixture. If the reaction is carried out under pressure in a bomb,rotation of the bomb will provide adequate mixing.

The pressure of carbon monoxide is not cirtical; however, inasmuch asthe carbon monoxide reacts mole for mole with the {Ly-unsaturatedaliphatic halide, it will of course be used in an amount of at least onemole per mole of the halide. The pressure of carbon monoxide can rangefrom about 1 to about 300 atmospheres. The preferred pressure is withinthe range from about to about 90 atmospheres.

The reaction proceeds at moderate temperatures, ranging from roomtemperature up to about 250 C. The upper limit of reaction temperatureis not critical and will be determined by the decomposition temperatureof the reactants and reaction products. At temperatures below 20 C., thereaction rate may be slow, but such temperatures can also be used. Anoptimum reaction rate is obtained within the range from about 35 toabout 110 C.

An inert organic solvent can be used as a diluent and to provide theliquid phase in the case where the fl,y-un saturated aliphatic halide isa gas or a solid. The reaction medium is preferably anhydrous, and,accordingly, anhydrous solvents should be used. Satisfactory solventsinclude the aliphatic and aromatic hydrocarbons, such as hexane, octane,decane, dodecane, petroleum ethers, benzene, toluene, xylene, andmesitylene; the chlorinated aliphatic hydrocarbons, such as ethylchloride, butyl chloride, and 1,2-dichloroethane; ethers such as ethylether and dimethoxyethane; and phosphines, such as tributyl phosphine.

The molar ratio of the 1,3-dienic olefin to Byy-unsaturated aliphatichalide is important in order to ensure preferential addition of theolefin to the allylic halide.

The molar ratio should preferably be less than about 2. Most preferably,the weight ratio is within the range from about 0.25 to about 4 parts ofthe 1,3-dienic olefin per part of the allylic halide. At ratios ofgreater than 2 to 1, 1,3-dienic olefins tend to produce increasingamounts of 3-alkenoyl halide as a by-product with the 3,7-dienoylhalide.

At the conclusion of the reaction, the product is recovered byseparating the catalyst by filtration or by centrifugal separation. Anyinert solvent and unreacted [iv-unsaturated aliphatic halide is removedby distillation, and the residue, which is the higher boiling3,7-dienoyl halide, is recovered.

The process is particularly adapted for continuous op eration, in whichcase the catalyst, liq-unsaturated aliphatic halide, any solvent, andthe 1,3-dienic olefin are blended and cycled to a reactor where they arecombined with carbon monoxide, held in the reactor for the requiredtime, and then separated as before. The reactor can, if desired, be inelongated form with the traverse time equal to the reaction time. Anyunreacted [Ly-unsaturated aliphatic halide can be recycled to thestarting material.

The following examples, in the opinion of the inventor, representpreferred embodiments of his invention.

EXAMPLE 1 Palladous chloride (12.3 millimoles), allyl chloride (1.05moles), and 1,3-butadiene (0.97 mole) were placed in the glass liner ofa rocking autoclave. Carbon monoxide was added to an initial pressure of34 atmospheres. The reactor contents were rocked and heated at 71 C. for41.5 hours. The excess pressure was then vented, and the bomb contentsfiltered to separate the catalyst. The product, an unsaturated acidchloride, was 3,7-octadienoyl chloride.

The filtrate was esterified with methanol at 0 C. An ether solution ofthe unsaturated methyl ester was hydrogenated using a 5% palladiumcarbon catalyst. The ether solution was freed of catalyst and thenconcentrated. The saturated products were identified by vapor phasechromatography. Methyl octanoate was produced in 23% yield, and methylvalerate in 3 yield.

EXAMPLE 2 A reaction was carried out as in Example 1, but using 2.3moles of 1,3-butadiene, 0.905 mole of allyl chloride, and 14.6millimoles of palladous chloride. The reaction was carried out at 74 C.for twenty-four hours under an initial carbon monoxide pressure ofatmospheres. The yield of 3,7-octadienoyl chloride was 25%. The yield of3-pentenoyl chloride was 24%.

The process of the invention can be used to prepare 3,7-dienoyl halidesthat are very difficult to prepare by other methods. These dienoylhalides are useful in the normal manner of acyl halides in that theyundergo hydrolysis to form the corresponding dienoic acids and undergoesterification with alcohols to form the corresponding dienoic esters.These can be hydrogenated, if desired, to the saturated acid chlorides,acids, and esters. Furthermore, the unsaturated groups make it possiblefor them to undergo epoxidation reactions, so that they can form diepoxyesters or unsaturated monoepoxy esters and acids. They can also bepolymerized by themselves or with other reactive monomers to formcomplex polymers of varying types and are useful cross-linking agentsfor linear polymers.

6 Having regard to the foregoing disclosure, the followfrom about 35 C.to about 110 C. and at a pressure ing is claimed as the inventive andpatentable embodiments within the range of 35 to 90 atmospheres.thereof: 3. A process in accordance with claim 1, in which the 1. Aprocess for preparing 3,7-dienoy1 halides which molar ratio of thecompounds of the formula comprises reacting a halide of the generalformula: Rm Ru Rm R R1 R3 R4 Rr- =CC=C-R14 3: and R1\ R R4 C5 CX with acompound of the formula:

R2 R5 g i is less than about 2: 1, respectively. 4. A process inaccordance with claim 1 in which the in which R R R R R R R R R R andamount of the catalyst is within the range from about R14 are selelctedzi i cogsisfigg i g 15 0.001 to about molar percent, based on the weightof an alkyl group having from 1 to 9 carbon atoms, the compound of theformula an aryl group having from 6 to 30 carbon atoms, an aralkyl oralkaryl group wherein the alkyl group l has up to 15 carbon atoms, andhaving from 1 to 5 20 of such substituents per aryl nucleus, R2 R5 3cycloalkyl group having from 6 to 30 carbon atoms 5. A process inaccordance with claim 1 in which the an alkyl substituted cycloalkylgroup with from 6 to 30 compound of the formula carbon atoms in thecycloalkyl group and in which each alkyl substituent has up to about 15carbon R Ila 111 1'2 atoms an halogen-substituted alkyl or cycloalkylgroup in RB C CCCRM which said halogen is selected from the groupconlslbutadlene' sisting of chlorine, bromine, fluorine and iodine,Process of clalfn 1 wherein the reactfmts are an estel. subsfitutedalkyl, aryl cycloalkyl group, the 1,3-butad1ene, allyl chloride andcarbon monoxide, and

ester substituent having the form COOR, wherein R the catalyst palladouschlonde' can be any of the moieties defined above for R R R R and Rhydrogen excepted; References Clted and wherein X is a halogen selectedfrom the group con- UNITED STATES PATENTS sisting of chlorine, bromine,fluorine and iodine 5 ,14 ,25 19 4 chiusoli 2 0 454 and carbon monoxide3,290,397 12/1966 Rust et a1. 260-654 in the present of a catalystselected from the group 3,309,403 3/1967 M d t; 1

consisting of metals of the group consisting of plat- 3,338,961 8/1967Closs0n et a1.

inum, palladium, osmium, iridium, rhodium, and 3,361,311 1/1968 Ih t 1,

ruthenium, the chlorides, bromides, nitrates, sulfates, 40

acetates and oxides of said metals, the organic com- FOREIGN PATENTSplexes of said metals with members of the group con- 803 463 10/1958Great Britain sisting of benzonitrile,'bis-1r allyl and acetylacetonate,

palladous benzoate, bis (benzonitrile) palladous chlo- OTHER REFERENCESride, palladous cyanide, rubidium carbonate, and po tassiumchloropalladite, at a temperature within the T511 et Jour' Amer Chem- 86(1964) range of 20 C.-250 C. and at a pressure within 43504353 the rangeof 1 to 300 atmospheres. 2. A process in accordance with claim 1, inwhich the LEON ZITVER Primary Exammer reaction is carried out attemperatures within the range H. T. MARS, Assistant Examiner

